Pre-treatment of lignocellulosic feeds for the production of glycols

ABSTRACT

A process for the preparing glycols from a lignocellulosic solid biomass involves contacting the biomass with an organic solvent comprising a low boiling point alcohol and a pre-treatment acid at a temperature in a range from 80 to 220° C. and a pressure in a range from 1 to 50 bara. The resulting mixture, having &gt;20 wt. % water, is separated into a pre-treated solid residue comprising cellulose and a liquid stream comprising dissolved lignin and hemicellulose. The pre-treated solid residue is subjected to a hydrogenolysis reaction, generating a glycols stream, a lights stream, comprising a first portion of organic solvent, and a heavies stream. At least of part of the liquid stream is separated to produce a second portion of organic solvent and a solid residue of lignin and hemicellulose. At least part of the first and second portion of organic solvent is recycled to the contacting step.

TECHNICAL FIELD

The present invention relates to a process for converting alignocellulosic feed stock into glycols. More specifically, the presentinvention relates to an integrated process for the pre-treatment of alignocellulose to deliver a cellulosic residue that has a reduced amountof lignin which may be fed to a hydrogenolysis process.

BACKGROUND

Ethylene glycol and propylene glycol are valuable materials with amultitude of commercial applications, e.g. as heat transfer media,antifreeze, and precursors to polymers, such as PET. Ethylene andpropylene glycols are typically made on an industrial scale byhydrolysis of the corresponding alkylene oxides, which are the oxidationproducts of ethylene and propylene, produced from fossil fuels.

In recent years, increased efforts have focused on producing chemicals,including glycols, from renewable feedstocks, such as plant and/orsugar-based materials. The conversion of sugars to glycols can be seenas an efficient use of the starting materials with the oxygen atomsremaining intact in the desired product.

Lignocellulosic solid biomass is viewed as an abundant renewableresource for chemicals due to the presence of sugars in the cell wallsof plants. More than 50% of the organic carbon on the earth's surface iscontained in plants. Lignocellulosic solid biomass is comprised ofhemicelluloses, cellulose and smaller portions of lignin and protein.These structural components are comprised primarily of pentose andhexose sugar monomers. Cellulose is a polymer comprised mostly ofcondensation polymerized glucose and hemicellulose is a polymer thatconsists of a variety of hexose and/or pentose sugars, for examplemostly xylose. These sugars can be converted into valuable components,provided they can be liberated from the cell walls and polymers thatcontain them. However, plant cell walls have evolved considerableresistance to microbial, mechanical or chemical breakdown to yieldcomponent sugars. In order to overcome recalcitrance, ground biomass isaltered by a variety of processes known as pretreatment. The aim of thepretreatment is to hydrolyze the hemicellulose, break down theprotective lignin structure and disrupt the crystalline structure ofcellulose. All of these steps enhance accessibility to the celluloseduring the subsequent hydrolysis (saccharification) step.

Organosolv pretreatment removes all or a portion of lignin upstream ofdownstream processes. This pretreatment involves the addition of organicsolvents, such as ethanol, to lignocellulosic feedstock to extract thelignin.

For the production of cellulose in pulp and paper production, cellulosicbiomass can be heated in a solvent comprising formic acid. InWO-A-97/26403 for example, a process is described for producing pulpfrom reed canary grass by subjecting the grass to a formic acid cookingstep, optionally followed by a bleaching step.

The saccharification of the cellulose holds promise of greater yields ofsugars under milder conditions and is therefore considered by many to bemore economically attractive. The recalcitrance of the raw biomass tohydrolysis necessitates a pretreatment to enhance the susceptibility ofthe cellulose to hydrolytic catalysts. A number of pretreatment methods,such as described by Mosier, et al. [Bioresource Technology, Vol. 96,pp. 673-686 (2005)], have been developed to alter the structural andchemical composition of biomass to improve conversion. Such methodsinclude treatment with a dilute acid steam explosion, as described inU.S. Pat. No. 4,461,648, hydrothermal pretreatment without the additionof chemicals as described in WO 2007/009463 A2, ammonia freeze explosionprocess as described by Holtzapple, M. T., et al. [Applied Biochemistryand Biotechnology, 28/29, pp. 59-74], and an organosolv extractionprocess described in U.S. Pat. No. 4,409,032. Despite these approaches,such pretreatment has been cited as the most expensive process inbiomass-to-fuels conversion [Ind. Eng. Chem. Res., Vol. 48(8), 3713-3729(2009)].

One pretreatment that has been extensively explored is a hightemperature, dilute-sulfuric acid (H₂SO₄) process, which effectivelyhydrolyzes the hemicellulosic portion of the biomass to soluble sugarsand exposes the cellulose so that saccharification is successful. Theparameters which can be employed to control the conditions of thepretreatment are time, temperature, and acid loading. These are oftencombined in a mathematical equation termed the combined severity factor.In general, the higher the acid loading employed, the lower thetemperature or the shorter the reaction time that can be employed; thiscomes at the cost of acid and a need to recycle the acid. Conversely,the lower the temperature, the longer the pretreatment process takes;this comes at the cost of productivity. However, the use of the higherconcentrations of acid requires lowering the pretreatment temperaturesbelow that where furfural formation becomes facile [B. P. Lavarack, etal., Biomass and Bioenergy, Vol. 23, pp. 367-380 (2002)] once againrequiring the recovery of the strong acid. If dilute acid streams andhigher temperatures are employed in the pretreatment reaction, the acidpassing downstream to the hydrolysis and subsequent fermentation stepsmust be neutralized resulting in inorganic salts which complicatesdownstream processing and requires more expensive waste water treatmentsystems. This also results in increased chemical costs for acid and baseconsumption.

These pretreatments have generally been designed to provide pulp orenable hydrolysis and fermentation of the cellulosic sugars. However,these pretreatments may impact sugar hydrogenolysis processes which havespecific characteristics and sensitivities. For example, sugarhydrogenolysis uses a metal catalyst that is sensitive toelectronegative elements, such as sulfur, chlorine and possibly nitrogentypically found in lignocellulosic feedstock. Sugar hydrogenolysis alsooperates at various pH and are therefore sensitive to acidic and basicimpurities present in the lignocellulosic feedstock or provided by thepretreatment.

Katarina Fabicovicova et al. “From Barley 1,2,4-15 Straw to ValuablePolyols: A Sustainable Process Using Ethanol/Water Mixtures andHydrogenolysis over Ruthenium-Tungsten Catalyst”, ChemSusChem, vol. 9,pages 2804-2815, 2016, discloses a process in which a lignocellulosicfeedstock was pre-treated with ethanol/water mixtures. The content oflignin in the biomass decreased for most samples. The influence of wateron hemicellulose liquefaction was also studied. After the pre-treatmentthe biomass material was subjected to hydrogenolysis over a Ru-W/ACcatalyst. The formation of undesired side-products is discussed in thisarticle.

Therefore, it would be advantageous to provide an improved pre-treatmentmethod for the production of glycols from lignocellulosic feedstock toreduce lignin, amino acids and ash.

SUMMARY

Accordingly, the present invention provides a process for thepreparation of glycols from a lignocellulosic solid biomass comprisingcellulose, hemicellulose and lignin in a reactor system, said processincluding: a) contacting the lignocellulosic solid biomass with anorganic solvent comprising a low boiling point alcohol and apre-treatment acid at a temperature ranging from about 80 to about 220°C. and a pressure ranging from 1 to 50 bar (absolute) for a time rangingfrom about 5 minutes to about 2 hours to obtain a first mixture; b)separating the first mixture obtained in step (a) into a pre-treatedsolid residue comprising cellulose and a liquid stream comprisingdissolved lignin and hemicellulose; c) subjecting the pre-treated solidresidue to a hydrogenolysis reaction and generating a glycols stream, alights stream and a heavies stream; d) recycling at least a part of thelights stream to step (a), wherein the lights stream comprises a firstportion of the organic solvent; e) separating at least of part of theliquid stream from step b) to produce a second portion of the organicsolvent and a solid residue that comprises lignin and hemicellulose; andf) recycling at least a part of the second portion of the organic tostep (a), wherein the first mixture has greater than about 20 wt %water, wherein the pre-treatment acid comprises at least one selectedfrom the group consisting of formic acid, acetic acid, propionic acid,butyric acid, glycolic acid, lactic acid, and combinations thereof whichis/are at least partially generated in-situ in step (a); and wherein atleast a part of the pre-treatment acid is recycled to step (a).

Additional features, advantages, and embodiments of the disclosedsubject matter may be set forth or apparent from consideration of thefollowing detailed description, drawings, and claims. Moreover, it is tobe understood that both the foregoing summary and the following detaileddescription are examples and are intended to provide further explanationwithout limiting the scope of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawing, which is included to provide a furtherunderstanding of the disclosed subject matter, is incorporated in andconstitutes a part of this specification. The drawing also illustratesembodiments of the disclosed subject matter and together with thedetailed description serves to explain the principles of embodiments ofthe disclosed subject matter. No attempt is made to show structuraldetails in more detail than may be necessary for a fundamentalunderstanding of the disclosed subject matter and various ways in whichit may be practiced.

FIG. 1 shows a block flow process scheme according to an embodiment ofthe disclosed subject matter.

FIG. 2 shows a block flow process scheme used in Example 12.

DETAILED DESCRIPTION

The following description of the variations is merely illustrative innature and is in no way intended to limit the scope of the disclosure,its application, or uses. The description and examples are presentedherein solely for the purposes of illustrating the various embodimentsof the disclosure and should not be construed as a limitation to thescope and applicability of the disclosure.

The terminology and phraseology used herein is for descriptive purposesand should not be construed as limiting in scope. Language such as“including,” “comprising,” “having,” “containing,” or “involving,” andvariations thereof, is intended to be broad and encompass the subjectmatter listed thereafter, equivalents, and additional subject matter notrecited.

Also, as used herein any references to “one embodiment” or “anembodiment” means that a particular element, feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. The appearances of the phrase “in oneembodiment” in various places in the specification are not necessarilyreferring to the same embodiment.

It has now been found that a solid lignocellulosic solid biomass can betreated by contacting it with an organic solvent and water at atemperature ranging from about 80 to about 220° C. to provide apre-treated solid residue which is subjected to hydrogenolysis reactiongenerating a glycols stream.

The treatment (or pre-treatment) may be included in a process for thepreparation of glycols from a lignocellulosic solid biomass comprisingcellulose, hemicellulose and lignin in a reactor system, said processincluding (a) contacting the lignocellulosic solid biomass with anorganic solvent comprising a low boiling point alcohol and apre-treatment acid at a temperature ranging from about 80 to about 220°C. and a pressure ranging from 1 to 50 bar (absolute) for a time rangingfrom about 5 minutes to about 2 hours to obtain a first mixture; (b)separating the first mixture obtained in step (a) into a pre-treatedsolid residue comprising cellulose and a liquid stream comprisingdissolved lignin and hemicellulose; (c) subjecting the pre-treated solidresidue to a hydrogenolysis reaction and generating a glycols stream, alights stream and a heavies stream; (d) recycling at least a part of thelights stream to step (a), wherein the lights stream comprises a firstportion of the organic solvent; (e) separating at least of part of theliquid stream from step b) to produce a second portion of the organicsolvent and a solid residue that comprises lignin and hemicellulose; and(f) recycling at least a part of the second portion of the organic tostep (a), wherein the first mixture has greater than about 20 wt %water, wherein the pre-treatment acid comprises at least one selectedfrom the group consisting of formic acid, acetic acid, propionic acid,butyric acid, glycolic acid, lactic acid, and combinations thereof whichis/are at least partially generated in-situ in step (a); and wherein atleast a part of the pre-treatment acid is recycled to step (a).

The pre-treatment acid comprises at least one selected from the groupconsisting of formic acid, acetic acid, propionic acid, butyric acid,glycolic acid, lactic acid, and combinations thereof which is/are atleast partially generated in-situ in step (a). At least a part of thepre-treatment acid is recycled to step (a). The pre-treatment acid maybe recovered from one or more solid and/or one or more liquid streams ofthe process. Recovery may be performed by means of washing, drying,heating, reducing pressure, electrodialysis, membrane separation,reversed osmosis, or combinations thereof.

The process advantageously produces cellulose suitable for hydrolysisinto sugars, which in turn can be processed into glycols.

The process according to an embodiment allows the separation oflignocellulose into cellulose, hemi-cellulose (and its breakdownproducts) and high quality lignin. In particular, the lignin andhemicellulose are separated from the cellulose and then further treatedto produce depolymerized lignin and an aqueous hemicellulose stream. Thedepolymerized lignin may be employed to form thermosetting resinproducts with carbonyl compounds such as formaldehyde, through thephenolic hydroxyl-groups and active sites on the aromatic ring. Thehemicellulose may be employed to form furfural.

The present process thus not only converts the cellulose andhemicellulose into valuable intermediates or final products, but alsoproduces lignin which can be employed as a chemical intermediate ratherthan as fuel only.

Pre-treatment: In step (a), a lignocellulosic solid biomass is contactedwith an organic solvent and a pre-treatment acid to obtain a firstmixture. The first mixture may include a pre-treated solid residue and aliquid. The first mixture may be termed a “pulping slurry.” Thecontacting of step (a) may be done in any reactor or other meanssuitable for the reaction and capable of operating under the conditionsof step (a). The organic solvent comprises water and a low boiling pointalcohol. The low boiling point alcohol preferably comprises at least oneselected from the group of methanol, ethanol, iso-propanol, n-propanol,and combinations thereof. During step (a) the pH of the lignocellulosicsolid biomass, the organic solvent, and the pre-treatment acid solutionpreferably is maintained in the range from about 2 to about 6. The pH ofthe obtained first mixture in step (a) preferably is in the range fromabout 2 to about 6.

Pretreatment step (a) may be carried out in any reactor configurationsuitable for solid-liquid contact, for example a co-current,counter-current of flow-through configuration. The conditions in thereactor include a temperature in the range of from about 80 to about220° C., preferably of from about 100 to about 170° C., more preferablyof from about 105 to about 150° C. Preferably, pretreatment step (a) iscarried out at a pressure in the range of from about 1 to about 50 bar,preferably of from about 2 to about 25 bar, more preferably of fromabout 3 to about 10 bar. Pre-treatment at atmospheric pressure isparticularly preferred.

In some embodiments, the organic solvent may also include apre-treatment acid of at least one of an organic acid, an inorganicacid, or mixtures thereof. The organic acid may be at least one selectedfrom the group consisting of α-hydroxysulfonic acids, formic acid,acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid,citric acid, benzoic acid, and combinations thereof. The inorganic acidmay be selected from the group consisting of hydrochloric acid, sulfuricacid, boric acid, nitric acid, phosphoric acid and mixtures thereof.

The lignocellulosic solid biomass will be contacted with the organicsolvent and the pre-treatment acid for a time period sufficient toachieve at least partial hemicellulose hydrolysis and/or partialdelignification, typically in the range of from about 0.5 to about 10hours, preferably in the range of from about 5 minutes to about 2 hours.In other embodiments, the time may be greater than about 10 minutes,greater than about 30 minutes, greater than about 60 minutes or lessthan about 3 hours, less than about 2 hours or less than about 1 hour.

The lignocellulosic solid biomass-to-the organic solvent andpre-treatment acid ratios both should preferably be in the range of fromabout 1:3 to about 1:50, preferably of from about 1:5 to about 1:20. Insome embodiments, the pulping slurry also includes water. Thelignocellulosic solid biomass will contain water due to the moisturetherein. In other embodiments, the pulping slurry may also optionallyinclude recycled liquid stream(s) obtained from step (c) and/or (e). Thepulping solution may further contain organic compounds known to besuitable organic solutions for organosolv processes. Examples of suchsolvents may include methanol, ethanol, iso-propanol, n-propanol acetoneas well as esters such as methyl acetate, ethyl acetate, n-propylacetate and isopropyl acetate.

In some embodiments, the organic solvent has a moisture content lessthan about 90 wt %, less than about 75 wt %, and less than about 50 wt%. In other embodiments, the organic solvent has a moisture contentgreater than 0 wt %, greater than about 15 wt %, and greater than about30 wt %. In some embodiments, the pulping slurry has a ratio of at leastabout 1:1 of organic solvent to water. In other embodiments, the pulpingslurry has a mass ratio of at least about 2:1 of organic solvent towater. In some embodiments, the pulping slurry has a mass ratio of atleast about 3:1 of organic solvent to water. The pulping slurry containsless than about 20 wt %, more preferably less than about 10 wt % of acidcomponents. The pulping slurry contains greater than about 20 wt %,preferably greater than about 30 wt %, and more preferably greater thanabout 45 wt % of water. The pulping slurry preferably contains less thanabout 75 wt % water.

Any suitable lignocellulosic solid biomass may be used in embodiments ofthe process according to the invention. Examples of suitable biomass areagricultural wastes such as corn stover, soybean stover, corn cobs, ricestraw, rice hulls, oat hulls, corn fibre, cereal straw like wheat,barley, rye, and oat straw; grasses such as switch grass, miscanthus,cord grass, rye grass, reed canary grass; forestry biomass such as woodand saw dust; recycled paper or pulp fibres; sugar processing residuessuch as bagasse and beet pulp. Cereal straw, especially wheat straw, isparticularly preferred. Prior to step (a), the solid biomass istypically comminuted into pieces or particles of a small size,preferably pieces or particles with an average length of less than about3 cm, more preferably an average length in the range of from about 0.5to about 2.5 cm.

In pre-treatment step (a), at least part of the hemicellulose ishydrolyzed and removed from the solid biomass. Also, part of the ligninis removed from the solid biomass. Thus, the cellulose is made moreaccessible for subsequent hydrolysis thus improving its digestibility.While not wishing to be bound by any theory, a minimum amount of waterhydrolyzes the carbohydrate-lignin bonds and solubilizes the basic ash.The organic solvent solubilizes hemicellulose, lignin and amino acids.In a preferred embodiment, the organic solvent is a light co-product ofa subsequent hydrogenolysis reaction, e.g. ethanol or propanol. In someembodiments, the pre-treatment acid acts as a catalyst and may begenerated in-situ. The pre-treatment acid may be a carboxylic acid suchas, but not limited to, acetic acid. The pre-treatment acid may berecovered from the pre-treated solid residue by heating and/or reducingthe pressure to produce an acid-removed pre-treated solid residue andthe liquid stream. The pre-treatment acid removed from the pre-treatedsolid residue may then be recycled to step (a). The pre-treatment acidmay be recycled to step (a) along with at least a part of the lightsstream.

In a preferred embodiment the pre-treatment acid comprises at least oneselected from the group consisting of formic acid, acetic acid,propionic acid, butyric acid, glycolic acid, lactic acid, andcombinations thereof which is/are at least partially generated in-situin step (a).

In some embodiments, the pre-treatment acid may also include an organicacid, an inorganic acid, or mixtures thereof. The organic acid may be atleast one selected from the group consisting of a-hydroxysulfonic acids,formic acid, acetic acid, propionic acid, butyric acid, glycolic acid,lactic acid, citric acid, benzoic acid, and combinations thereof. Theinorganic acid may be selected from the group consisting of hydrochloricacid, sulfuric acid, boric acid, nitric acid, phosphoric acid andmixtures thereof.

The pulping slurry contains less than about 20 wt %, more preferablyless than about 10 wt % of acid components. If the pre-treatment acid isa strong acid such as, but not limited to, sulfuric acid, the pulpingsolution may contain 0 wt %, greater than about 0.1 wt % and less thanabout 5 wt %, less than about 1 wt %, or less than about 0.5 wt % acid.If the pre-treatment acid is a weak acid such as, but not limited to,acetic acid, the pulping solution may contain 0 wt %, greater than about1 wt %, greater than wt %, greater than about 10 wt % and less thanabout 50 wt %, less than about 35 wt %, or less than about 20 wt % acid.In a preferred embodiment, the pre-treatment acid does not includenon-volatile inorganic acids but only volatile organic acids, which mayfacilitate the cleaning of the lignin by evaporation. In otherembodiments, if the lignin contains non-volatile acids and/or sugars,the lignin will need a water wash and a drying step, e.g. after solventevaporation. As used in this description, strong acids have a pKa<−1.74.An example of a strong acid is hydrochloric acid (HCl), whose pKa is−6.3.

Solid recovery and wash: In step (b), the first mixture obtained in step(a) is separated into a pre-treated solid residue including celluloseand a liquid stream including dissolved lignin and hemicellulose. Thisseparation can be carried out by any suitable technique known in theart, for example filtration or centrifugation. The separation in step(b) preferably is performed by pressing the mixture in a suitable pressfilter, screw press, rotary drum or any other means suitable to separatea solid/liquid mixture that is highly corrosive and highly viscous atthe reaction conditions. Examples for suitable means include conveyerbelts, screw presses, extruders, centrifuges. Preferably a screw pressis used. In some embodiments, the liquid stream includes lignin, ash andacid. In some embodiments, the liquid stream is recycled to step (a).This liquid stream may be recycled with or without any furtherprocessing.

Steps (a) and (b) may be integrated, preferably when operating theprocess continuously. Both steps may happen simultaneously, e.g. in ascrew press. The liquid stream(s) obtained in step (b) may be referredto herein as black liquor.

In some embodiments, the pre-treated solid residue may be sent to stepc) without washing and/or drying. However, in other embodiments, inorder to remove remaining organic solvent, pre-treatment acid andlignin/hemicellulose from the pre-treated solid residue, step (b) mayfurther comprise one or more optional washing steps with a washingliquid such as water, acetic acid, the organic solvent, thepre-treatment acid, or an otherwise suitable aqueous stream, such as arecycle stream obtained from step (c) and/or (e) stream, to removeresidual hemi-cellulose and lignin from the pre-treated solid residue.In some embodiments, the washing liquid may be a combination of waterand the aqueous recycle from steps (c) and/or (e) may be used. Inanother embodiment, the pre-treated solid residue is washed with a freshmedium comprising acetic acid. The washing step occurs in a counter flowor cross flow manner In some embodiments, the washing liquid iscompatible with components of the hydrogenolysis step which follows.

The washing liquid preferably comprises less than 50 vol % water,preferably less than 40 vol % water. In order to improve lignin removal,the washing liquid may further comprise acetic acid. Pure water oracetic acid/water mixtures are particularly suitable washing liquids.More than one washing steps may be carried out, for example a firstwashing step with an acetic acid/water mixture followed by one or morewashing steps with water only or several washing steps with water only.The washing step(s) may be typically carried out at a temperature in therange of from ambient to about 100° C., preferably of from about 20 toabout 90° C.

After each or all of the optional washing step(s), the obtained mixturemay be separated into a liquid stream and washed pre-treated solidresidue. The liquid stream, including dissolved and hydrolyzedhemicelluloses, lignin, residual organic solvent and pre-treatment acidfrom the pre-treated solid residue may be sent for further processing instep (e) or may be recycled in part to step (a).

In some embodiments, step (b) may optionally further contain a secondstep wherein the liquid content of the pre-treated solid residue isfurther reduced. After the pre-treated solid residue is separated fromthe liquid stream, the pre-treated solid residue typically has a solidscontent of about 50 wt %. However, in order to increase theeffectiveness of further processing, the solids content preferably isincreased to at least 65 wt %, preferably more than 65 wt %, morepreferably at least 70 wt % This is preferably done by the use of an airblower or dryer.

Hydrogenolysis: The pre-treated solid residue obtained in step (b) isnext subjected to a hydrogenolysis reaction in step (c). Thehydrogenolysis reaction includes contacting the pre-treated solidresidue, a soluble retro-Aldol catalyst, and optionally a hydrogenolysisacid in a reactor under hydrogenation conditions, with a heterogeneoushydrogenation catalyst. Product streams from the hydrogenolysis reactioninclude a glycols stream, a lights stream and a heavies stream may beobtained from the reactor.

The hydrogenolysis acid may be one of a low-molecular weight organicacid, a carbonic acid, a mineral acid, and combinations thereof. Thelow-molecular weight organic acid may be at least one of: formic acid,acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid,citric acid, benzoic acid, and combinations thereof. The mineral acidmay be at least one of: sulfuric acid, phosphoric acid, boric acid, andcombinations thereof. In some embodiments, the pre-treatment acid andhydrogenolysis acid are the same.

The soluble retro-Aldol catalyst may comprise one or more compounds,complex or elemental material comprising tungsten, molybdenum, vanadium,niobium, chromium, titanium or zirconium. In particular, the solubleretro-Aldol catalyst may comprise one or more materials selected fromthe list consisting of tungstic acid, molybdic acid, ammonium tungstate,ammonium metatungstate, ammonium paratungstate, tungstate compoundscomprising at least one Group I or II element, metatungstate compoundscomprising at least one Group I or II element, paratungstate compoundscomprising at least one Group I or II element, heteropoly compounds oftungsten, heteropoly compounds of molybdenum, tungsten oxides,molybdenum oxides, vanadium oxides, metavanadates, chromium oxides,chromium sulfate, titanium ethoxide, zirconium acetate, zirconiumcarbonate, zirconium hydroxide, niobium oxides, niobium ethoxide, andcombinations thereof. The metal component is in a form other than acarbide, nitride, or phosphide. According to an embodiment, examples ofthe soluble retro-Aldol catalyst may include at least one of: silvertungstate, sodium tungstate, sodium meta-tungstate, ammoniummeta-tungstate, sodium poly-tungstate, tungstic acid, alkali- andalkaline-earth metal tungstates, sodium phospho-tungstate,phospho-tungstic acid, alkali- and alkaline-earth metalphospho-tungstates, alkali- and alkaline-earth metal molybdates, alkali-and alkaline-earth metal phospho-molybdates, phospho-molybdic acid,heteropoly acids, mixed tungstates and molybdates, niobic acid,silicotungstic acid, alkali- and alkaline-earth metal niobates. In anaspect, the soluble retro-Aldol catalyst may be sodium tungstate.

In some embodiments, heterogeneous hydrogenation catalysts may besupported or un-supported metal catalysts selected from Group 8 to Group11 metals in the periodic table. Examples of un-supported metalcatalysts are Raney-metal catalysts such as Raney-Ni, Raney-Co,Raney-Cu, and Raney-Ru, and metal-powder catalysts such as powdered Ni,Co, Cu, Cu—Zn, Cu—Cr, Ni—Mo, Ni—W, and Ni—Cr. The heterogeneoushydrogenation catalyst may be promoted with metals such as Al, Fe, Cr,Mn, Co, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, In, Sn, Sb, and Pb.One or more metals may be used in the formulation of the promoted metalcatalysts. The promoting metals may be present in concentrations rangingfrom about 0.001 wt % to about 10 wt %. Examples of supported-metalhydrogenation catalysts are Group 8 to Group 11 metal catalystssupported on hydrothermally stable supports such as TiO₂, ZrO₂, andalpha-alumina. The metals may be used individually or in combinationwith one or more of the other metals.

According to an embodiment, at least one of the heterogeneoushydrogenation catalyst and soluble retro-Aldol catalyst is supported ona solid support. In an embodiment, any other active catalyst componentmay be present in either heterogeneous or homogeneous form. In thiscase, any other active catalyst component may also be supported on asolid support. In one embodiment, the heterogeneous hydrogenationcatalyst is supported on one solid support and the soluble retro-Aldolcatalyst is supported on a second solid support which may comprise thesame or different material. As a specific example, the heterogeneoushydrogenation catalyst may be a hydrogenation catalyst supported on ahydrothermally stable support. In another embodiment, both theheterogeneous hydrogenation catalyst and soluble retro-Aldol catalystare supported on one solid hydrothermally stable support.

The solid support may be in the form of a powder or in the form ofregular or irregular shapes such as spheres, extrudates, pills, pellets,tablets, monolithic structures. Alternatively, the solid supports may bepresent as surface coatings, for examples on the surfaces of tubes orheat exchangers. Suitable solid support materials are those known to theskilled person and include, but are not limited to aluminas, silicas,zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon,activated carbon, zeolites, clays, silica alumina and mixtures thereof.

In some embodiments, the hydrogenolysis reaction may also include areaction solvent. The reaction solvent may be water, a C1 to C6 alcohol,a C1 to C6 polyol, or mixtures thereof. Further reaction solvents mayalso be added to the reactor in a separate feed stream or may be addedto the carbohydrate feed before it enters the reactor. Examples of Cl toC6 polyols include 1,2-hexanediol, glycerol, etc. As an example, thereaction solvent may be a mixture including water and at least one ofalcohols, ethers, and ether-alcohols, and mixtures thereof. In anembodiment, the reaction solvent may be water.

Step (c) may be performed under hydrogenation conditions to maximize thedesired yield of glycols. For example, the hydrogenation conditions mayinclude temperature, pressure, flow rate, and any other process variablethat may be controlled. In an embodiment, the hydrogenation conditionsmay include a temperature in the range of from about 180 to about 250°C. and from about 200 to about 250° C. The hydrogenation conditions mayalso include a pressure in the range of from about 35 to about 140 bar.The residence time in the hydrogenation reactor vessel of may be atleast about 1 minute, at least about 2 minutes, and at least about 5minutes. Suitably the residence time in the hydrogenation reactor vesselis no more than about 5 hours, no more than about 2 hours, and no morethan about 1 hour. According to an implementation, the average residencetime in the hydrogenation reactor vessel is no more than about 2 hours.

In an embodiment, step (c) may also include contacting the pre-treatedsolid residue with hydrogen. Hydrogen may be supplied into the reactorvessel under pressure in a manner common in the art. In an example, themethod of step (c) takes place in the absence of air or oxygen. In orderto achieve this, it is preferable that the atmosphere in the reactorvessel be evacuated and replaced with hydrogen repeatedly, after loadingof any initial reactor vessel contents, and before the reaction starts.

In some embodiments, prior to the pre-treated solid residue obtained instep (b) entering the hydrogenolysis reaction in step (c), thepre-treated solid residue may be subjected to enzymatic hydrolysis. Theenzymatic hydrolysis transforms some of the cellulose in the pre-treatedsolid residue into glucose which is fed into the hydrogenolysisreaction. The cellulose in the pre-treated solid residue may be moreaccessible and thus may improve its enzymatic digestibility. Suitableenzymes and process conditions for enzymatic hydrolysis are known in theart, for example from WO2006/034590 or Lynd et al., Microbial CelluloseUtilization: Fundamentals and Biotechnology, Microbiology and MolecularBiology Reviews, 66 (2002), p 506-577.

According to the presently disclosed subject matter, multiple productstreams may be obtained from step (c) including a glycols stream, alights stream and a heavies stream. The separation of the productstreams is known to one skilled in the art. The glycols stream mayinclude at least about 5 wt % concentration of glycols. In addition, theglycols stream may represent a yield from saccharides of at least about60 wt % glycols, and at least about 70 wt % glycols. In an embodiment,the glycols stream may represent a yield from saccharides of at leastabout 60 wt % ethylene glycol, and at least about 65 wt % ethyleneglycol. An advantage of the presently disclosed method is the ability tomaximize the yield of ethylene glycol relative to the yield of propyleneglycol. For example, the glycols stream may include an ethyleneglycol/propylene glycol wt % yield ratio of at least about 1:1, anethylene glycol/propylene glycol wt % yield ratio of at least about 7:1,and an ethylene glycol/propylene glycol wt % yield ratio of at leastabout 10:1. In addition, the presently disclosed method allows forminimizing undesired products of the subject reaction. Accordingly, theglycols stream may include a yield of no more than about 10 wt %sorbitol. Further, the glycols stream may include a yield of less thanabout 3 wt % 1,2-butanediol. Additionally, the glycols stream mayinclude a minimum ethylene glycol/1,2-butanediol wt % yield ratio ofabout 20:1, thereby maximizing the ethylene glycol yield relative toother less desired products.

According to an embodiment, the glycols stream may be further processed.For example, the glycols stream may be fed to a second reactor forcontacting with hydrogen in the presence of a heterogeneoushydrogenation catalyst. A final product stream comprising ethyleneglycol may be obtained that is substantially free of compoundscontaining carbonyl functional groups. The heterogeneous hydrogenationcatalyst used in this further processing of the glycols stream may ormay not be the same heterogeneous hydrogenation catalyst used in thebi-functional catalyst system in the glycols production process.

Recycle: In some embodiments, after the hydrogenolysis reaction in step(c), at least a portion of the lights stream is recycled to step (a) forcontacting with the lignocellulosic solid biomass in step (d). Thelights stream may include a first portion of the organic solvent . Insome embodiments, the lights stream may also include a portion of thepre-treatment acid. In some embodiments, the organic solvent is aby-product from the hydrogenolysis reaction. Thus, the first portion ofthe organic solvent supplements the organic solvent initially added instep (a).

In some embodiments, after the hydrogenolysis reaction in step (c), atleast a portion of the heavies stream is recycled back to step (c). Insome embodiments, the heavies stream includes the retro-Aldol catalyst.Thus, the portion of the heavies stream supplements the retro-Aldolcatalyst initially added in step (c). In some embodiments, the heaviesstream includes the hydrogenolysis acid. Thus, the portion of theheavies stream supplements the hydrogenolysis acid initially added instep (c).

In some embodiments, the process also includes separating at least ofpart of the liquid stream from step b) to produce a second portion ofthe organic solvent and a solid residue that comprises lignin andhemicellulose in step (e). The separation in step (e) preferably isperformed by heating the liquid stream to a temperature ranging fromabout 50° C. to about 150° C. The separation in step (e) may also beperformed by numerous methods known by one skilled in the art. Thesecond portion of the organic solvent may be recycled to step (a) instep (f). In some embodiments, the second portion of the organic solventmay also include a portion of the pre-treatment acid. In someembodiments, the lignin stream includes at least about 80 wt % lignin,more preferably about 90 wt % lignin, and most preferably about 95 wt %lignin. In some embodiments, the lignin from step (e) is ready to beused without further processing, for example as a starting material forthermosetting resins.

In some cases, the solid residue is washed with water to solubilize thehemicellulose and leave behind a solid lignin. The aqueous hemicellulosemay be converted to furfural using a process such as that disclosed inU.S. Pat. No. 10,0870,160 and U.S. Patent Publication 20190144409, theentirety of which are hereby incorporated by reference.

In some cases, the lignin solid from step (e) may contain inorganicacid, sugars (hemicellulose) and/or ash (from the biomass). The ligninsolid may be washed with water and then dried to remove thesecontaminants The washed lignin may be free of carbohydrates, microbialbiomass (dead cells, proteins, cell membranes, etc.), inorganics (ash)and light organic solvents and is sometimes referred to as “highquality” lignin. In particular, the lignin may be employed to formthermosetting resin products with carbonyl compounds such asformaldehyde, through the phenolic hydroxyl-groups and active sites onthe aromatic ring.

FIG. 1 shows an embodiment of a block flow process scheme according toan implementation of the disclosed subject matter. Lignocellulosicmaterial 1 is placed in vessel 100. Organic solvent 2 and apre-treatment acid 3 are also added to the vessel 100. The vessel 100operates at temperatures ranging from about 80 to about 220° C.,pressures ranging from 1 to 50 bar (absolute) for a time ranging fromabout 5 minutes to about 2 hours. A first mixture 4 is obtained and fedto a separator 200. The first mixture 4 is separated into a pre-treatedsolid residue 5 and a liquid stream 6. The pre-treated solid residue 5is fed to reactor 300 for hydrogenolysis. The products from the reactor300 include a glycols stream 7, a lights stream 8 and a heavies stream9. A portion 10 of the lights stream 8 may be recycled back to vessel100. The portion 10 of the lights stream may include a portion oforganic solvent and a portion of the pre-treatment acid, whichsupplement the organic solvent 2 and the pre-treatment acid 3 initiallyadded to the vessel 100. A portion 11 of the heavies stream 9 may berecycled back to reactor 300. In some embodiments, an additional stream17 is fed to the reactor 300. The additional stream 17 may comprise oneor more of the retro-Aldol catalyst, the hydrogenolysis acid or amixture of both. The heavies stream may include a portion of thehydrogenolysis catalyst. The liquid stream 6, including lignin,hemicellulose, organic solvent, ash and acid may be separated into alignin/hemicellulose solid stream 12 and an organic solvent and acidstream 13. The organic solvent and acid stream 13 supplements theorganic solvent 2 and the pre-treatment acid 3 initially added to thevessel 100. The lignin/hemicellulose solid stream 12 may be washed withwater 14 to produce an aqueous hemicellulose stream 15 and a solidlignin product 16.

Examples 1-2

Embodiments of the process are designed for the use and recycle of anorganic co-solvent and/or acid catalyst that may be generated from thebiomass feedstock. This example demonstrates experimentally topossibility to produce glycols with good yield by pre-treatinglignocellulosic biomass according to the invention.

Examples 1 and 2: Pretreatment—Biomass pretreatment was performed in a200 mL stirred autoclave. The autoclave is equipped with a pressuresensor and two thermocouples (bottom and top of reactor respectively).The autoclave is positioned in a metal block which is equipped withcartridge heaters & copper tubing (heating & cooling by convection).

In a typical experiment the reactor was charged with 10 grams of biomass(Poplar wood, 4 wt % moisture content, sieve fraction 1-2 mm) and 90grams of solvent. The solvent consists of mixtures of water:ethanol orwater: acetic acid, as reported below. The reactor was sealed, followedby a leak test with nitrogen at ˜30bar. The autoclave was flushed withnitrogen 3 times (pressurized till 30 bar N₂, depressurized/N₂ vented,repeated 3 times). Finally, the autoclave was pressurized with 3 bar N₂to ensure inert atmosphere and proper sealing of the inlet valve. Thestirrer was started and the reactor was heated by the cartridge heater.After the reactor temperature (Temperature measured in the bottom/liquidphase) attained the desired reaction temperature (180° C. or 200° C., asreported below) it was kept at this desired temperature 1 to 5 hours (asreported below). After the desired reaction time the autoclave wasactively cooled by means of a water cooled copper tubing.

The autoclave was opened and the slurry (solid residue and solvent) werefiltered over a 5 μm wire mesh. Additional solvent was forced out of thesolid cake. When no more solvent could be recovered, the solid cake wasremoved and dried in the fume hood for several days.

After drying the solid residue was washed with a mixture of 50/50water/ethanol until no colour change was observed. Subsequently thesolid residue was dried by nitrogen flushing until no weight change ofthe solid residue was observed.

Hydrogenolysis—The hydrogenolysis experiments are performed in a 45 mLautoclave. The reactor is mounted on a pneumatic arm. A preheatedfluidized bed and water bath allowed for rapid heating and coolingrespectively. The autoclave is equipped with a pressure transducer and athermocouple located in the bottom of vessel. The reactor was stirred bya hollow shaft stirrer. Characteristics of the biomass feedstocks arepresented in the table below.

TABLE 1 Biomass feedstocks Feedstocks Poplar Wood Cellulose (aftergrinding) (Avicel PH101) Particle size (pm) <53 ~50 Saccharide content,wt % 70 100

Typically, the reactor was charged with 14.25 g of solvent, 0.75 g ofbiomass, 0.02 g of retro-aldol catalyst (sodium polytungstate), 0.086 gof hydrogenation catalyst (Raney-Ni, dry basis) and 0.3 g acetic acidand some NaOH to buffer the solution to pH 3.3. Raney-Ni was thoroughlywashed with demi-water until the pH became neutral. The reactor wassealed and a leak test with nitrogen at ˜120 bar was performed. Theautoclave was flushed with nitrogen 2 times by pressurization to 120bar. Subsequently, the autoclave was flushed with hydrogen 2 times bypressurization with hydrogen to 60 bar. The stirrer was started (1300rpm) and the autoclave submerged in the fluidized bed. After the reactortemperature attained the desired reaction temperature of 245° C. it waskept at this desired temperature for 2 hours. After the desired reactiontime the autoclave was actively cooled by submerging it in a water bath.

When the autoclave attained room temperature it was depressurized,whereby the gas was collected in water displacement vessel. The vesselallows for direct quantification of the gas volume. The gas compositionwas determined by GC (at least 3 injections). Hereafter the reactor wasopened, and the reactor content was transferred to a glass bottle. Asample was taken and subjected to HPLC analysis. Remaining catalyst andunconverted residue were collected in a separate bottle by flushing thereactor with demineralized water.

HPLC analysis was performed on an Agilent 1200 series (Hi-Plex-H+column)operated at 65° C. running 5 mM H₂SO₄ as eluent (0.6 ml min⁻¹). Thesamples were filtered (Whatman 0.2 μm filter) prior to HPLC analysis.Optionally; samples were diluted with mili-q water prior to HPLCanalysis. Standards were prepared for; Ethylene glycol, propyleneglycol, glycerol, 1,2 butanediol, methanol, ethanol, 1-propanol,2-propanol, erythritol, sorbitol, mannitol.

The hydrogenolysis yields are expressed as wt % of the polysaccharidespresent in the biomass used as feed for the hydrogenolysis.

TABLE 2 Products Example 1 2 Comp 1 Comp 2 Comp 3 Pre-treatmentconditions T (° C.) 180 200 n/a n/a n/a time (min) 300 180 n/a n/a n/abiomass (wt %) 10 10 n/a n/a n/a Type Poplar Poplar Poplar Avicel AvicelWater (wt. %) 45 45 n/a n/a n/a Ethanol (wt. %) 0 45 n/a n/a n/a Aceticacid (wt. %) 45 0 n/a n/a n/a Pre-treatment results Solid residue yield61 63 n/a n/a n/a (wt %) polysaccharide content 89 94 76 100 100 (wt %)(100-lignin) Hydrogenolysis yields (wt % on polysaccharide)Ethylene-glycol (wt. %) 31.8 26.5 7.7 31.7 32.7 Propylene-glycol (wt. %)7.4 7.7 11.7 7.1 5.5 Sorbitol + Mannitol 9.6 5.1 6.5 17.5 15.2 (wt. %)1.2-Butanediol (wt %) 8.4 4.1 4.4 6.1 6.2 Glycerol (wt %) 1.6 2.0 2.41.7 1.4 m-Erythritol (wt %) 2.7 1.9 1.7 3.7 3.9 Xylitol (wt %) 0.7 1.66.0 n.d. 1.2 Sum (wt %) 62.1 48.8 40.4 67.8 66.1 Conversion (wt %) 68 6677 78 n.d.

The Comparative examples 2 and 3 (Avicel) where were evaluated induplicate show very high EG and PG yield of ˜32 wt % and 5-7 wt %,respectively. In contrast, Comparative example 1 (untreated poplar)gives very low yields of EG and PG ˜8 and 12 w % respectively, while thepulp obtained by pre-treatment Examples 1 and 2 (poplar) with aceticacid gives much higher yields of EG and PG, namely 26-31 and 7-8 wt %,respectively.

Examples 3-5

The following examples illustrate ways to define a target for solventrecovery to match the amount of solvent that can be produced from thebiomass during the process and, thereby, avoid the need for purchasingfresh solvent. While not being bound by any theory, the purpose of therecycle is to compensate for the inevitable losses which occur duringthe process without importing additional co-solvent or acid. The matchof the make-up to the losses may be described in the equations below:

Make up [kg/h]>losses [kg/h]

Solvent yield [g solvent/g feed] * feed concentration [g feed/gsolution] >solvent lost fraction [g lost/g solvent] * solventconcentration [g solvent/g solution]Which is identical to

Yield/lost fraction>feed concentration/solvent concentration

Example 3 (loss of alcohol solvent): The digester feed solution consistsof 10 wt % biomass and 45 wt % alcohol solvent, the remaining 45 wt %being water. The hydrogenolysis of the carbohydrate yields 10 wt % inalcohol solvents (ethanol +propanol) and the carbohydrates account for70 wt % of the biomass. Accordingly, the maximum solvent amounts to:

Solvent loss fraction <(0.1*0.7*0.1)/0.45<1.5 wt %

Consequently, >98.5 wt % of the solvent that is fed to the biomassdigester will have to be recovered at some point in the process.

Example 4 (loss of acetic acid): The digester feed solution consists of10 wt % biomass and 45 wt % acetic acid, the remaining 45 wt % beingwater. The digestion of the biomass yields 5 wt % of acetic acid.Accordingly, the maximum solvent amounts to:

Loss fraction <(0.05*0.1)/0.45<1.1 wt %

Consequently, >98.9 wt % of the acetic acid that is fed to the biomassdigester will have to be recovered at some point in the process.

The pH of a solution of water:acetic acid in 1:1 weight ratio is veryacidic and thereby suitable for biomass digestion. With a pKa of 4.76for acetic acid, this solution can be calculated to have a pH of about1.6.

Example 5 (loss of solvent and acetic acid): The digester feed solutionconsists of 10 wt % biomass, 25 wt % alcohol solvent and 20 wt % aceticacid, the remaining 45 wt % being water. The digestion of the biomassyields 5 wt % of acetic acid and the hydrogenolysis of the carbohydrateyields 10 wt % in alcohol solvents (ethanol and propanol) and thecarbohydrates account for 70 wt % of the biomass. Accordingly, themaximum solvent loss amounts to:

Solvent Loss fraction <(0.1*0.7*0.1)/0.25<2.8 wt %

Acid Loss fraction <(0.05*0.1)/0.2<2.5 wt %

Consequently, >97.2 wt % of the solvent and >97.5 wt % of the aceticacid that is fed to the biomass digester will have to be recovered atsome point in the process. This also means that the fraction of organicadditive, i.e. solvent+acid, that needs to be recovered amountsto >(2.8%*0.25+2.5%*0.2)/(0.25+0.2)>2.7 wt %.

Examples 3-5 show stringent solvent and acid recovery targets, thereby,confirming the need for designing a process with excellent recoverypotential. The experienced practitioners will know how to adjust theseloss criteria for the exact configuration of the process.

Examples 6-7

The examples 6-7 propose options to further reduce the energy demand ofthe solvent recovery.

Example 6 (effect of biomass loading): Another parameter for the processis too achieve high biomass loading. This can be achieved directly byusing a higher biomass/solvent ratio, e.g. 20 wt % compared to the 10 wt% mentioned in previous examples. The expert will recognize that, basedon the equations proposed earlier, a doubling of the biomass loadingwill result in a doubling of the solvent loss that is acceptable. Such adoubling of the biomass loading will also result in a doubling(approximately) of the process throughput, all equipment remaininglargely unaffected. This will result in a reduction of investment andenergy cost per ton of biomass processed (or pulp produced) by about50%.

Example 7 (solvent recycling prior to recovery): The above can also beachieved indirectly by recovering the solvent after L/S separation andrecycling part of it directly to the digestor, with dissolved lignin andhemicellulose products, while the remaining part is sent to the work-upsection to recover the solvent from the lignin and dissolvedhemicellulose. This may reduce the need of clean solvent and, thereby,allow higher solvent loss. For instance, one can envisage splitting theliquid product (after L/S separation) in two equivalent fractions, onebeing directly recycled to the digester with lignin and cellulose, theother being send to an evaporation unit to recover the solvent, aceticacid and water (from lignin and cellulose) and recycle this purifiedliquid stream also the digester. Expert in the art will recognize thesuch a scheme will reduce the evaporation duty by 50% and will result ina build-up of lignin and cellulose in the liquid product by about 2times.

Examples 8-11 Pretreatment and Hydrogenolysis Experiments Pre-Treatment

A reactor (a 200 ml stirred autoclave) was charged with 10 g of poplarwood (oven dried at 105° C., sieve fraction 1-2 mm) and 90 g of solvent.The solvent used in Example 8 was a water and ethanol mixture. InExamples 9 to 11 mixtures of a water and acetic acid were used. Oxygenwas removed by nitrogen flushing. The pre-treatment of the poplar woodwith the solvent was carried out for 1-5 h at 180-200° C. Afterwards,the solid residue was washed with a mixture of 50/50 w/w water/ethanoluntil no colour change of the liquid was observed. Subsequently, thesolid residue was dried by flushing nitrogen at room temperature untilno weight change of the solid residue was observed. The composition ofthe resulting biomass samples, to be used as feedstock for thehydrogenolysis experiments, is presented.

Hydrogenolysis

Catalytic hydrogenolysis experiments were carried out in a 45 ml batchautoclave. A preheated fluidized sand bed and a water bath allowed forrapid heating and rapid cooling, respectively. The autoclave wasequipped with a hollow shaft stirrer, a pressure transducer and athermocouple located on the bottom of vessel.

The reactor was charged with 14.25 g of deionised water, 0.75 g ofbiomass, 0.021 g of retro-aldol catalyst (sodium polytungstate), 0.086 gof hydrogenation catalyst (Raney-Ni, dry basis) and 0.3 g of acetic acidplus NaOH to buffer the solution to pH 3.3. Prior to use, Raney-Ni wasthoroughly washed with deionized water until the pH of the washing waterbecame neutral. The reactor was sealed and flushed twice with nitrogen,twice with hydrogen and pressurized to about 60 bar. The stirrer wasthen started (1300 rpm) and the autoclave submerged in the fluidizedsand bed. The reaction time was started once the reactor attained atemperature of 245° C.

The residence time was limited to 1 h, as no further glycol yieldincrease was observed at longer residence times.

After completion the autoclave was rapidly cooled applying a water bathand depressurized, opened and the reactor content obtained. A liquidsample was taken and subjected to high performance liquid chromatography(HPLC) analysis and pH measurement (Metrohm LL Unitrode Pt 1000 pH).Remaining catalyst and unconverted residue were collected in a separatebottle by flushing the reactor with deionized water.

TABLE 3 Example 8 9 10 11 Pretreatment conditions Feedstock PoplarPoplar Poplar Poplar Temperature (° C.) 200 180 180 180 Reaction time(min) 180 300 60 60 Solvent Ethanol Acetic Acetic Acetic acid Acid AcidSolvent fraction (wt. %) 50 50 70 89.3 Water fraction (wt. %) 50 50 3010.7 Mixture biomass & solvent Biomass loading (wt. %) 9.3 9.6 9.6 9.6Composition - pre- treated,washed and dried Cellulose (wt. %) 77.6 79.283.1 77.5 Hemi-cellulose (wt. %) 5.9 6.5 3.2 6.7 Total(poly)-saccharides 83.5 85.8 86.4 84.2 (wt. %) Total lignin (wt. %) 6.211.5 3.6 1.5

TABLE 4 Example 8 9 10 11 Hydrogenolysis conditions Temperature (° C.)245 245 245 245 Residence time (min) 60 60 60 60 Solid loading (wt %) 55 5 5 Feedstock Particle Size (mm) 0.05 0.05 0.05 0.05 Raney Nickel (g)0.086 0.086 0.086 0.086 SPT (Na6W12O39) (g) 0.021 0.021 0.021 0.021Initial H2 Pressure (bar) 61.0 60.8 60.0 59.9 Final reactor pressure(bar) 47.3 50.3 51.3 51.9 Final pH 3.3 3.2 3.3 3.4 Product Yields(poly)-alcohols Ethylene-glycol (wt. %) 25.1 28.3 32.3 21.2Propylene-glycol (wt. %) 7.3 6.6 6.8 9.1 1.2-Butanediol (wt %) 3.9 7.56.1 6.2 1.2-Hexanediol (wt. %) 0.34 0.86 0.26 0.47 Glycerol (wt %) 1.91.4 2.5 2.4 m-Erythritol (wt %) 1.8 2.4 4.5 2.9 Xylitol (wt. %) 1.5 0.61.3 1.4 Sorbitol + Mannitol (wt. %) 4.8 8.6 17.9 15.9 Light alcoholsMethanol 0.90 2.5 1.7 2.7 Ethanol 5.3 4.4 4.0 5.0 1-Propanol 0.76 0.710.47 0.92 2-Propanol 0.86 1.71 0.23 1-Butanol 0.09 0.06 0.14 2-Butanol0.5 0.8 0.3 0.6 Light-Alcohols, total (% w) 8.5 10.2 6.6 9.5

The hydrogenolysis was performed using biomass that was pre-treated withwater/alcohol or with water/acid, followed by washing and drying.

Light alcohols were formed during hydrogenolysis. The light alcohols maybe recycled to step (a).

Example 12

FIG. 2 shows a block scheme that may be used after the block scheme ofFIG. 1. Reactor effluent 7, obtained by hydrogenolysis of glucose (seeFIG. 1), is depressurized in a gas/liquid separator 701, to separate avapor phase stream 702 from a liquid stream 703. The liquid stream 703is cooled in heat exchanger 704 providing a feed stream 705 which is fedinto a distillation column 706. A stream of non-condensing components707 and condensing components mainly comprising light alcohols 708 isobtained from the upper part of the column. The bottom stream 709 can befurther processed to obtain purified components.

The total organics fraction in this particular example is 42.7% w instream 7. The combined fraction of methanol, ethanol, 1-propanol,2-propanol, 1-butanol and 2-butanol is 2.7% w, which represents 6.4% wof the total organics fraction.

Aspen(+) modeling results of stream compositions are presented in Table5. Stream 708 is mainly composed of light alcohols, with 15% waterpresent. The majority of the light alcohols are recovered in stream 702(after condensation, not described in further detail) and in stream 708(Table 5).

This example shows that a mixture of light alcohols can be recovered andrecycled. This does not require large amounts of energy or complexequipment.

The recovered mixture of light alcohols is useful for recycle in aprocess as claimed (see also FIG. 1). Lignin will dissolve in it.

TABLE 5 Aspen(+) modeling results, stream compositions (mass fractions).Stream description 7 702 703 705 707 708 709 Phase Mixed Vapor LiquidLiquid Vapor Liquid Liquid Temperature (deg. C.) 203 186 186 165 40 40195 Pressure (bara) 100 12 12 12 12 12 12 Mass Flows (t/year) 1000 45.9954.1 954.1 0.031 13.1 940.9 Mass Fractions methanol 0.0038 0.01350.0033 0.0033 0.0126 0.0688 0.0024 ethanol 0.0125 0.0630 0.0101 0.01010.0511 0.4755 0.0036 1-propanol 0.0102 0.0549 0.0081 0.0081 0.01480.2996 0.0040 2-propanol 4.46E−05 0.000334038 3.06E−05 3.06E−050.000196061 0.0021491 1.10E−06 1-butanol 0.0006 0.0033 0.0005 4.66E−041.15E−05 0.0005 0.0005 2-butanol 3.48E−05 0.0003 2.39E−05 2.39E−057.63E−05 0.0016 1.73E−06 H2O 0.5549 0.7708 0.5445 0.5445 0.0091 0.15000.5500 H2 4.97E−04 1.07E−02 8.02E−06 8.02E−06 0.2143 7.78E−05 0 methane1.36E−03 0.0289 3.67E−05 3.67E−05 0.6368 0.0012 0 ethane 1.66E−04 0.00354.63E−06 4.63E−06 0.0375 0.0002 0 propane 2.30E−04 0.0049 5.97E−065.97E−06 0.0234 0.0004 0 MEG 0.2802 0.0324 0.2921 0.2921 0 0 0.2962 MPG0.0281 6.47E−03 0.0292 2.92E−02 0 0 0.0296 1,2-butanediol 0.00471.24E−03 0.0049 4.92E−03 0 0 0.0050 1,2-pentanediol 0.0003 7.34E−050.0003 2.73E−04 0 0 0.0003 1,2-hexanediol 0.0135 0.0039 0.0139 0.0139 00 0.0141 glycerol 0.0057 2.80E−05 0.0060 5.99E−03 0 0 0.0061 erythritol0.0283 7.68E−06 0.0297 0.0297 0 0 0.0301 sorbitol 0.0340 2.08E−08 0.03563.56E−02 0 0 0.0361 isosorbide 0.0024 7.55E−05 0.0025 2.54E−03 0 00.0026 acetic acid 0.0004 2.77E−04 0.0004 4.38E−04 0 0 0.0004 lacticacid 0.0002 8.98E−06 0.0003 0.0003 0 0 0.0003

TABLE 6 Component recovered from feed (% recovered). DescriptionRecovered from feed (% w) 702 703 705 707 708 709 702 + 708 methanol16.4 83.6 83.6 0.0 23.8 59.8 40.2 ethanol 23.1 76.9 76.9 0.0 49.9 27.073.0 1-propanol 24.7 75.3 75.3 0.0 38.4 36.9 63.1 2-propanol 34.4 65.665.6 0.0 63.2 2.3 97.7 1-butanol 25.5 74.5 74.5 0.0 1.1 73.4 26.62-butanol 34.5 65.5 65.5 0.0 60.8 4.7 95.3 H2O 6.4 93.6 93.6 0.0 0.493.3 6.7 H2 98.5 1.5 1.5 1.3 0.2 0.0 98.7 methane 97.4 2.6 2.6 1.4 1.10.0 98.6 ethane 97.3 2.7 2.7 0.7 2.0 0.0 99.3 propane 97.5 2.5 2.5 0.32.2 0.0 99.7 MEG 0.5 99.5 99.5 0.0 0.0 99.5 0.5 MPG 1.1 98.9 98.9 0.00.0 98.9 1.1 1,2-butanediol 1.2 98.8 98.8 0.0 0.0 98.8 1.21,2-pentanediol 1.3 98.7 98.7 0.0 0.0 98.7 1.3 1,2-hexanediol 1.3 98.798.7 0.0 0.0 98.7 1.3 glycerol 0.0 100.0 100.0 0.0 0.0 100.0 0.0erythritol 0.0 100.0 100.0 0.0 0.0 100.0 0.0 sorbitol 0.0 100.0 100.00.0 0.0 100.0 0.0 isosorbide 0.1 99.9 99.9 0.0 0.0 99.9 0.1 acetic acid2.9 97.1 97.1 0.0 0.0 97.1 2.9 lactic acid 0.2 99.8 99.8 0.0 0.0 99.80.2

As shown in the Examples section above, the presently disclosed methodfor pre-treating lignocellulosic-containing feedstock has numerousadvantages over the prior art. Therefore, the disclosed subject matterprovides an improved method suitable for the pre-treatment oflignocellulosic-containing feedstock for the use in production ofglycols.

The foregoing description, for purpose of explanation, has beendescribed with reference to specific embodiments. However, theillustrative discussions above are not intended to be exhaustive or tolimit embodiments of the disclosed subject matter to the precise formsdisclosed. Many modifications and variations are possible in view of theabove teachings. The embodiments were chosen and described in order toexplain the principles of embodiments of the disclosed subject matterand their practical applications, to thereby enable others skilled inthe art to utilize those embodiments as well as various embodiments withvarious modifications as may be suited to the particular usecontemplated.

We claim:
 1. A process for the preparation of glycols from alignocellulosic solid biomass comprising cellulose, hemicellulose andlignin in a reactor system, said process comprising: a) contacting thelignocellulosic solid biomass with an organic solvent comprising a lowboiling point alcohol, and a pre-treatment acid, at a temperatureranging from about 80 to about 220° C. and a pressure ranging from 1 to50 bar (absolute) for a time ranging from about 5 minutes to about 2hours to obtain a first mixture; b) separating the first mixtureobtained in step (a) into a pre-treated solid residue comprisingcellulose and a liquid stream comprising dissolved lignin andhemicellulose; c) subjecting the pre-treated solid residue to ahydrogenolysis reaction and generating a glycols stream, a lights streamand a heavies stream; d) recycling at least a part of the lights streamto step (a), wherein the lights stream comprises a first portion of theorganic solvent; e) separating at least of part of the liquid streamfrom step b) to produce a second portion of the organic solvent and asolid residue that comprises lignin and hemicellulose; and f) recyclingat least a part of the second portion of the organic solvent to step(a); wherein the first mixture has greater than about 20 wt % water;wherein the pre-treatment acid comprises at least one selected from thegroup consisting of formic acid, acetic acid, propionic acid, butyricacid, glycolic acid, lactic acid, and combinations thereof which is/areat least partially generated in-situ in step (a); and wherein at least apart of the pre-treatment acid is recycled to step (a).
 2. The processof claim 1, wherein the pre-treated solid residue comprisespre-treatment acid and the process further comprises removingpre-treatment acid from the pre-treated solid residue by washing ,drying or combinations thereof to produce an acid-removed pre-treatedsolid residue and recycling the removed pre-treated acid to step (a);wherein drying preferably comprises heating, reducing pressure, orcombinations thereof.
 3. The process of claim 1, wherein the pre-treatedsolid residue comprises lignin and the process further comprisesremoving the lignin from the pre-treated solid residue by washing toproduce an lignin-removed pre-treated solid residue and recycling theremoved pre-treated acid to step (a).
 4. The process according to claim1, wherein the pre-treatment acid further comprises at least oneselected from the group consisting of hydrochloric acid, sulfuric acid,boric acid, nitric acid, phosphoric acid, hydroxysulfonic acid, citricacid, benzoic acid, α-hydroxysulfonic acids, and mixtures thereof. 5.The process according to claim 1, wherein the pH of the lignocellulosicsolid biomass, the organic solvent, and the pre-treatment acid solutionin step (a) is maintained in the range from 2-6.
 6. The processaccording to claim 1, wherein subjecting the pre-treated solid residueto a hydrogenolysis reaction comprises contacting the pre-treated solidresidue, a soluble retro-Aldol catalyst, and an optional hydrogenolysisacid in a reactor under hydrogenation conditions.
 7. The process ofclaim 6, wherein the pre-treatment acid and the hydrogenolysis acid arethe same.
 8. The process according to claim 1, wherein the separatingthe liquid stream (b) comprises evaporation by heating the liquid streamat a temperature in the range of from 50 to 150° C.
 9. The processaccording to claim 1, wherein the low boiling point alcohol is at leastone of methanol, ethanol, iso-propanol and n-propanol.
 10. The processaccording to claim 1, further comprising recycling at least a part ofthe heavies stream to step (c).
 11. The process according to claim 1,further comprising separating and/or washing the lignin/hemicellulosesolid to produce an aqueous hemicellulose stream and a lignin solid. 12.The process of claim 11, further comprising converting the aqueoushemicellulose stream to furfural.
 13. The process according to claim 1,wherein a part of the liquid stream form step (b) is recycled to step(a).